SELECTIVE SiN LATERAL RECESS

ABSTRACT

Exemplary methods for laterally etching silicon nitride may include flowing a fluorine-containing precursor and an oxygen-containing precursor into a remote plasma region of a semiconductor processing chamber. The methods may include forming a plasma within the remote plasma region to generate plasma effluents of the fluorine-containing precursor and the oxygen-containing precursor. The methods may also include flowing the plasma effluents into a processing region of the semiconductor processing chamber. A substrate may be positioned within the processing region, and the substrate may include a trench formed through stacked layers including alternating layers of silicon nitride and silicon oxide. The methods may also include laterally etching the layers of silicon nitride from sidewalls of the trench while substantially maintaining the layers of silicon oxide. The layers of silicon nitride may be laterally etched less than 10 nm from the sidewalls of the trench.

CROSS-REFERENCES TO RELATED APPLICATIONS

The application is a continuation of U.S. patent application Ser. No.15/288,898, filed Oct. 7, 2016, the entire contents of which are herebyincorporated by reference in their entirety for all purposes.

TECHNICAL FIELD

The present technology relates to semiconductor processes and equipment.More specifically, the present technology relates to laterally etchingsilicon nitride in vertical structures.

BACKGROUND

Integrated circuits are made possible by processes which produceintricately patterned material layers on substrate surfaces. Producingpatterned material on a substrate requires controlled methods forremoval of exposed material. Chemical etching is used for a variety ofpurposes including transferring a pattern in photoresist into underlyinglayers, thinning layers, or thinning lateral dimensions of featuresalready present on the surface. Often it is desirable to have an etchprocess that etches one material faster than another facilitating, forexample, a pattern transfer process. Such an etch process is said to beselective to the first material. As a result of the diversity ofmaterials, circuits, and processes, etch processes have been developedwith a selectivity towards a variety of materials.

Etch processes may be termed wet or dry based on the materials used inthe process. A wet HF etch preferentially removes silicon oxide overother dielectrics and materials. However, wet processes may havedifficulty penetrating some constrained trenches and also may sometimesdeform the remaining material. Dry etches produced in local plasmasformed within the substrate processing region can penetrate moreconstrained trenches and exhibit less deformation of delicate remainingstructures. However, local plasmas may damage the substrate through theproduction of electric arcs as they discharge.

Thus, there is a need for improved systems and methods that can be usedto produce high quality devices and structures. These and other needsare addressed by the present technology.

SUMMARY

Methods and systems for laterally etching silicon nitride may includeflowing a fluorine-containing precursor and an oxygen-containingprecursor into a remote plasma region of a semiconductor processingchamber. The methods may include forming a plasma within the remoteplasma region to generate plasma effluents of the fluorine-containingprecursor and the oxygen-containing precursor. The methods may alsoinclude flowing the plasma effluents into a processing region of thesemiconductor processing chamber. A substrate may be positioned withinthe processing region, and the substrate may include a trench formedthrough stacked layers including alternating layers of silicon nitrideand silicon oxide. The methods may also include laterally etching thelayers of silicon nitride from sidewalls of the trench whilesubstantially maintaining the layers of silicon oxide. The layers ofsilicon nitride may be laterally etched less than 10 nm from thesidewalls of the trench.

In embodiments a flow-rate ratio of oxygen-containing precursor tofluorine-containing precursor may be greater than or about 50:1. Thestacked layers of alternating materials may include at least 50 layersof alternating layers of silicon nitride and silicon oxide, and thetrench may be characterized by an aspect ratio of greater than or about100:1. In embodiments the lateral etching may be performed at atemperature of between about −100° C. and about 100° C., and may beperformed at a temperature less than or about 0° C. The lateral etchingmay be performed at a chamber operating pressure of less than or about 1Torr.

In some embodiments the layers of silicon nitride may be laterallyetched less than or about 6 nm. Additionally, the lateral etching mayinclude oxidizing a portion of the silicon nitride to produce afluorinated oxide. Fluorine within the fluorinated oxide may diffusethrough the oxidized portion of the silicon nitride to laterally etchthe silicon nitride. Additionally, the etching methods may furtherinclude removing the fluorinated oxide from the silicon nitride. Inembodiments removing the fluorinated oxide may include etching thefluorinated oxide with plasma effluents produced from afluorine-containing precursor and a hydrogen-containing precursor. Inembodiments a layer of silicon nitride at an upper region of the trenchand a layer of silicon nitride at a lower region of the trench maydiffer in lateral etch amounts by less than about 30%.

The present technology may also include etching methods that may includeflowing a fluorine-containing precursor and an oxygen-containingprecursor into a remote plasma region of a semiconductor processingchamber. The methods may include forming a plasma within the remoteplasma region to generate primary plasma effluents of thefluorine-containing and oxygen-containing precursors. The methods mayinclude flowing the primary plasma effluents into a processing region ofthe semiconductor processing chamber. A substrate may be positionedwithin the processing region, and the substrate may include a trenchformed through stacked layers including alternating layers of siliconnitride and silicon oxide. The methods may include oxidizing a portionof the silicon nitride from sidewalls of the trench to produce afluorinated oxide region in each layer of silicon nitride. The methodsmay also include flowing a fluorine-containing precursor into the remoteplasma region of the semiconductor processing chamber while generating aplasma to produce secondary plasma effluents. The methods may includeflowing the secondary plasma effluents into the processing region of thesemiconductor processing chamber. The methods may still further includelaterally etching the fluorinated oxide region from each layer ofsilicon nitride.

In exemplary methods a flow-rate ratio of oxygen-containing precursor tofluorine-containing precursor used to produce the primary plasmaeffluents may be greater than or about 60:1. In some embodiments, thesilicon nitride may be oxidized to a depth of from about 1 nm to about 8nm. A bottom of the trench may at least partially be oxidized along withthe layers of silicon nitride, and the bottom of the trench may beetched less than or about 5 nm. A temperature within the semiconductorprocessing chamber during exemplary etching methods may be less than orabout 0° C. Laterally etching the fluorinated oxide region from eachlayer of silicon nitride may further include flowing ahydrogen-containing precursor into the semiconductor processing chamber.The oxidized portion of silicon nitride may include a lower qualityoxide than the layers of silicon oxide. Additionally, in exemplarymethods a layer of silicon nitride at an upper region of the trench anda layer of silicon nitride at a lower region of the trench may differ inlateral etch amounts by less than about 20%.

Such technology may provide numerous benefits over conventional systemsand techniques. For example, the processes may provide finely reducedlayers within a memory hole. Additionally, the operations of embodimentsof the present technology may all be performed in a single chamber.These and other embodiments, along with many of their advantages andfeatures, are described in more detail in conjunction with the belowdescription and attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosedtechnology may be realized by reference to the remaining portions of thespecification and the drawings.

FIG. 1 shows a top plan view of one embodiment of an exemplaryprocessing system according to embodiments of the present technology.

FIG. 2A shows a schematic cross-sectional view of an exemplaryprocessing chamber according to embodiments of the present technology.

FIG. 2B shows a detailed view of a portion of the processing chamberillustrated in FIG. 2A according to embodiments of the presenttechnology.

FIG. 3 shows a bottom plan view of an exemplary showerhead according toembodiments of the present technology.

FIG. 4 shows exemplary operations in a method according to embodimentsof the present technology.

FIG. 5 shows exemplary operations in a method according to embodimentsof the present technology.

FIGS. 6A-6C show cross-sectional views of substrates being processedaccording to embodiments of the present technology.

Several of the figures are included as schematics. It is to beunderstood that the figures are for illustrative purposes, and are notto be considered of scale unless specifically stated to be of scale.Additionally, as schematics, the figures are provided to aidcomprehension and may not include all aspects or information compared torealistic representations, and may include superfluous or exaggeratedmaterial for illustrative purposes.

In the appended figures, similar components and/or features may have thesame reference label. Further, various components of the same type maybe distinguished by following the reference label by a letter thatdistinguishes among the similar components. If only the first referencelabel is used in the specification, the description is applicable to anyone of the similar components having the same first reference labelirrespective of the letter.

DETAILED DESCRIPTION

In transitioning from 2D NAND to 3D NAND, many process operations aremodified from vertical to horizontal operations. Additionally, as 3DNAND structures grow in the number of cells being formed, the aspectratios of memory holes and other structures increase, sometimesdramatically. During 3D NAND processing, stacks of placeholder layersand dielectric materials may form the inter-electrode dielectric or IPDlayers. These placeholder layers may have a variety of operationsperformed to place structures before fully removing the material andreplacing it with metal. While the metallization may be incorporated onone side of the cell structure, operations may have previously beenperformed on the other side of the structure, such as forming floatinggates or charge-trap layers. Although these layers may be formed withinthe memory hole, crosstalk between vertically separated memory cells mayoccur. One way to reduce this communication may include etching theplaceholder material before forming these layers to allow dielectricmaterial to further separate the individual cell material layers fromadjacent cells.

Because of the high aspect ratios of these memory holes, penetrating theentire length to access cells at the bottom of the hole may bedifficult. Conventional dry etch techniques may have difficulty withadequate diffusion of precursors to the bottom of the memory hole.Accordingly, the etchants often begin etching the top cell layers beforeeven reaching the bottom cell layers, which may not occur. This may endup producing a V-shape through the memory holes where substantialetching may have occurred at placeholder materials at or near the top ofthe memory hole, and minimal and sometimes no etching has been performedat or near the bottom of the memory hole. Accordingly, many conventionaltechnologies utilize a wet etch to access each of the cell placeholdermaterials to perform a lateral etch of placeholders before forminglayers, such as the charge-trap layer. However, wet etching may be morerobust than other etching techniques, and the wet etching may etch theplaceholder materials further than necessary or desired. For example,the wet etching may etch each layer more than 10 nm, and may etch eachlayer almost through completely to other memory holes, which may makeplacing the cell layers in the appropriate or desired location moredifficult, and may weaken the structures causing deformation.

The present technology overcomes these issues by performing a dry etchprocess that allows precursors to diffuse adequately through the cellmaterials before substantial etching has occurred at the upper regionsof the cell. By producing a type of barrier layer, etchants may beslowed to the point where full diffusion through the memory hole mayoccur. Thus, a similar etching profile may be formed through placeholdermaterials at the top of the memory hole and the bottom of the memoryhole, which may allow uniformly sized cells to be produced throughoutthe vertical stack, unlike other dry etch techniques. Additionally, theentire process may be performed in a single chamber, unlike wet etchtechniques that require transferring the processed substrate betweenmultiple chambers to perform the wet etch and then dry the substrate.

Although the remaining disclosure will routinely identify specificetching processes utilizing the disclosed technology, it will be readilyunderstood that the systems and methods are equally applicable todeposition and cleaning processes as may occur in the describedchambers. Accordingly, the technology should not be considered to be solimited as for use with etching processes or chambers alone. Moreover,although an exemplary chamber is described to provide foundation for thepresent technology, it is to be understood that the present technologycan be applied to virtually any semiconductor processing chamber thatmay allow the single-chamber operations described.

FIG. 1 shows a top plan view of one embodiment of a processing system100 of deposition, etching, baking, and curing chambers according toembodiments. In the figure, a pair of front opening unified pods (FOUPs)102 supply substrates of a variety of sizes that are received by roboticarms 104 and placed into a low pressure holding area 106 before beingplaced into one of the substrate processing chambers 108 a-f, positionedin tandem sections 109 a-c. A second robotic arm 110 may be used totransport the substrate wafers from the holding area 106 to thesubstrate processing chambers 108 a-f and back. Each substrateprocessing chamber 108 a-f, can be outfitted to perform a number ofsubstrate processing operations including the dry etch processesdescribed herein in addition to cyclical layer deposition (CLD), atomiclayer deposition (ALD), chemical vapor deposition (CVD), physical vapordeposition (PVD), etch, pre-clean, degas, orientation, and othersubstrate processes.

The substrate processing chambers 108 a-f may include one or more systemcomponents for depositing, annealing, curing and/or etching a dielectricfilm on the substrate wafer. In one configuration, two pairs of theprocessing chambers, e.g., 108 c-d and 108 e-f, may be used to depositdielectric material on the substrate, and the third pair of processingchambers, e.g., 108 a-b, may be used to etch the deposited dielectric.In another configuration, all three pairs of chambers, e.g., 108 a-f,may be configured to etch a dielectric film on the substrate. Any one ormore of the processes described may be carried out in chamber(s)separated from the fabrication system shown in different embodiments. Itwill be appreciated that additional configurations of deposition,etching, annealing, and curing chambers for dielectric films arecontemplated by system 100.

FIG. 2A shows a cross-sectional view of an exemplary process chambersystem 200 with partitioned plasma generation regions within theprocessing chamber. During film etching, e.g., titanium nitride,tantalum nitride, tungsten, silicon, polysilicon, silicon oxide, siliconnitride, silicon oxynitride, silicon oxycarbide, etc., a process gas maybe flowed into the first plasma region 215 through a gas inlet assembly205. A remote plasma system (RPS) 201 may optionally be included in thesystem, and may process a first gas which then travels through gas inletassembly 205. The inlet assembly 205 may include two or more distinctgas supply channels where the second channel (not shown) may bypass theRPS 201, if included.

A cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225,and a substrate support 265, having a substrate 255 disposed thereon,are shown and may each be included according to embodiments. Thepedestal 265 may have a heat exchange channel through which a heatexchange fluid flows to control the temperature of the substrate, whichmay be operated to heat and/or cool the substrate or wafer duringprocessing operations. The wafer support platter of the pedestal 265,which may comprise aluminum, ceramic, or a combination thereof, may alsobe resistively heated in order to achieve relatively high temperatures,such as from up to or about 100° C. to above or about 1100° C., using anembedded resistive heater element.

The faceplate 217 may be pyramidal, conical, or of another similarstructure with a narrow top portion expanding to a wide bottom portion.The faceplate 217 may additionally be flat as shown and include aplurality of through-channels used to distribute process gases. Plasmagenerating gases and/or plasma excited species, depending on use of theRPS 201, may pass through a plurality of holes, shown in FIG. 2B, infaceplate 217 for a more uniform delivery into the first plasma region215.

Exemplary configurations may include having the gas inlet assembly 205open into a gas supply region 258 partitioned from the first plasmaregion 215 by faceplate 217 so that the gases/species flow through theholes in the faceplate 217 into the first plasma region 215.

Structural and operational features may be selected to preventsignificant backflow of plasma from the first plasma region 215 backinto the supply region 258, gas inlet assembly 205, and fluid supplysystem 210. The faceplate 217, or a conductive top portion of thechamber, and showerhead 225 are shown with an insulating ring 220located between the features, which allows an AC potential to be appliedto the faceplate 217 relative to showerhead 225 and/or ion suppressor223. The insulating ring 220 may be positioned between the faceplate 217and the showerhead 225 and/or ion suppressor 223 enabling a capacitivelycoupled plasma (CCP) to be formed in the first plasma region. A baffle(not shown) may additionally be located in the first plasma region 215,or otherwise coupled with gas inlet assembly 205, to affect the flow offluid into the region through gas inlet assembly 205.

The ion suppressor 223 may comprise a plate or other geometry thatdefines a plurality of apertures throughout the structure that areconfigured to suppress the migration of ionically-charged species out ofthe first plasma region 215 while allowing uncharged neutral or radicalspecies to pass through the ion suppressor 223 into an activated gasdelivery region between the suppressor and the showerhead. Inembodiments, the ion suppressor 223 may comprise a perforated plate witha variety of aperture configurations. These uncharged species mayinclude highly reactive species that are transported with less reactivecarrier gas through the apertures. As noted above, the migration ofionic species through the holes may be reduced, and in some instancescompletely suppressed. Controlling the amount of ionic species passingthrough the ion suppressor 223 may advantageously provide increasedcontrol over the gas mixture brought into contact with the underlyingwafer substrate, which in turn may increase control of the depositionand/or etch characteristics of the gas mixture. For example, adjustmentsin the ion concentration of the gas mixture can significantly alter itsetch selectivity, e.g., SiNx:SiOx etch ratios, Si:SiOx etch ratios, etc.In alternative embodiments in which deposition is performed, it can alsoshift the balance of conformal-to-flowable style depositions fordielectric materials.

The plurality of apertures in the ion suppressor 223 may be configuredto control the passage of the activated gas, i.e., the ionic, radical,and/or neutral species, through the ion suppressor 223. For example, theaspect ratio of the holes, or the hole diameter to length, and/or thegeometry of the holes may be controlled so that the flow ofionically-charged species in the activated gas passing through the ionsuppressor 223 is reduced. The holes in the ion suppressor 223 mayinclude a tapered portion that faces the plasma excitation region 215,and a cylindrical portion that faces the showerhead 225. The cylindricalportion may be shaped and dimensioned to control the flow of ionicspecies passing to the showerhead 225. An adjustable electrical bias mayalso be applied to the ion suppressor 223 as an additional means tocontrol the flow of ionic species through the suppressor.

The ion suppressor 223 may function to reduce or eliminate the amount ofionically charged species traveling from the plasma generation region tothe substrate. Uncharged neutral and radical species may still passthrough the openings in the ion suppressor to react with the substrate.It should be noted that the complete elimination of ionically chargedspecies in the reaction region surrounding the substrate may not beperformed in embodiments. In certain instances, ionic species areintended to reach the substrate in order to perform the etch and/ordeposition process. In these instances, the ion suppressor may help tocontrol the concentration of ionic species in the reaction region at alevel that assists the process.

Showerhead 225 in combination with ion suppressor 223 may allow a plasmapresent in first plasma region 215 to avoid directly exciting gases insubstrate processing region 233, while still allowing excited species totravel from chamber plasma region 215 into substrate processing region233. In this way, the chamber may be configured to prevent the plasmafrom contacting a substrate 255 being etched. This may advantageouslyprotect a variety of intricate structures and films patterned on thesubstrate, which may be damaged, dislocated, or otherwise warped ifdirectly contacted by a generated plasma. Additionally, when plasma isallowed to contact the substrate or approach the substrate level, therate at which oxide species etch may increase. Accordingly, if anexposed region of material is oxide, this material may be furtherprotected by maintaining the plasma remotely from the substrate.

The processing system may further include a power supply 240electrically coupled with the processing chamber to provide electricpower to the faceplate 217, ion suppressor 223, showerhead 225, and/orpedestal 265 to generate a plasma in the first plasma region 215 orprocessing region 233. The power supply may be configured to deliver anadjustable amount of power to the chamber depending on the processperformed. Such a configuration may allow for a tunable plasma to beused in the processes being performed. Unlike a remote plasma unit,which is often presented with on or off functionality, a tunable plasmamay be configured to deliver a specific amount of power to the plasmaregion 215. This in turn may allow development of particular plasmacharacteristics such that precursors may be dissociated in specific waysto enhance the etching profiles produced by these precursors.

A plasma may be ignited either in chamber plasma region 215 aboveshowerhead 225 or substrate processing region 233 below showerhead 225.Plasma may be present in chamber plasma region 215 to produce theradical precursors from an inflow of, for example, a fluorine-containingprecursor or other precursor. An AC voltage typically in the radiofrequency (RF) range may be applied between the conductive top portionof the processing chamber, such as faceplate 217, and showerhead 225and/or ion suppressor 223 to ignite a plasma in chamber plasma region215 during deposition. An RF power supply may generate a high RFfrequency of 13.56 MHz but may also generate other frequencies alone orin combination with the 13.56 MHz frequency.

FIG. 2B shows a detailed view 253 of the features affecting theprocessing gas distribution through faceplate 217. As shown in FIGS. 2Aand 2B, faceplate 217, cooling plate 203, and gas inlet assembly 205intersect to define a gas supply region 258 into which process gases maybe delivered from gas inlet 205. The gases may fill the gas supplyregion 258 and flow to first plasma region 215 through apertures 259 infaceplate 217. The apertures 259 may be configured to direct flow in asubstantially unidirectional manner such that process gases may flowinto processing region 233, but may be partially or fully prevented frombackflow into the gas supply region 258 after traversing the faceplate217.

The gas distribution assemblies such as showerhead 225 for use in theprocessing chamber section 200 may be referred to as dual channelshowerheads (DCSH) and are additionally detailed in the embodimentsdescribed in FIG. 3. The dual channel showerhead may provide for etchingprocesses that allow for separation of etchants outside of theprocessing region 233 to provide limited interaction with chambercomponents and each other prior to being delivered into the processingregion.

The showerhead 225 may comprise an upper plate 214 and a lower plate216. The plates may be coupled with one another to define a volume 218between the plates. The coupling of the plates may be so as to providefirst fluid channels 219 through the upper and lower plates, and secondfluid channels 221 through the lower plate 216. The formed channels maybe configured to provide fluid access from the volume 218 through thelower plate 216 via second fluid channels 221 alone, and the first fluidchannels 219 may be fluidly isolated from the volume 218 between theplates and the second fluid channels 221. The volume 218 may be fluidlyaccessible through a side of the gas distribution assembly 225.

FIG. 3 is a bottom view of a showerhead 325 for use with a processingchamber according to embodiments. Showerhead 325 may correspond with theshowerhead 225 shown in FIG. 2A. Through-holes 365, which show a view offirst fluid channels 219, may have a plurality of shapes andconfigurations in order to control and affect the flow of precursorsthrough the showerhead 225. Small holes 375, which show a view of secondfluid channels 221, may be distributed substantially evenly over thesurface of the showerhead, even amongst the through-holes 365, and mayhelp to provide more even mixing of the precursors as they exit theshowerhead than other configurations.

The chambers discussed previously may be used in performing exemplarymethods including etching methods. Turning to FIG. 4 is shown exemplaryoperations in a method 400 according to embodiments of the presenttechnology. Prior to the first operation of the method a substrate maybe processed in one or more ways before being placed within a processingregion of a chamber in which method 400 may be performed. For example,IPD layers may be formed on the substrate and then one or more memoryholes or trenches may be formed through the stacked layers. The IPDlayers may include any number of materials, and may include alternatinglayers of a placeholder material and a dielectric material. Inembodiments the dielectric material may be or include silicon oxide, andthe placeholder material may be or include silicon nitride. Although theremaining disclosure will discuss silicon nitride and silicon oxide, anyother known materials used in these two layers may be substituted forone or more of the layers. Some or all of these operations may beperformed in chambers or system tools as previously described, or may beperformed in different chambers on the same system tool, which mayinclude the chamber in which the operations of method 400 are performed.

The method 400 may include flowing a fluorine-containing precursor andan oxygen-containing precursor into a remote plasma region of asemiconductor processing chamber at operation 405. An exemplary chambermay be chamber 200 previously described, which may include one or bothof the RPS unit 201 or first plasma region 215. Either or both of theseregions may be the remote plasma region used in operation 405. A plasmamay be generated within the remote plasma region at operation 410, whichmay generate plasma effluents of the fluorine-containing precursor andthe oxygen-containing precursor. The plasma effluents may be flowed to aprocessing region of the chamber at operation 415. The plasma effluentsmay interact with the substrate in the processing region, which mayinclude a trench formed through stacked layers of material, which mayinclude alternating layers of silicon nitride and silicon oxide, forexample, although other placeholder material and/or dielectric materialmay be used. The precursors may laterally etch the layers of siliconnitride at operation 420. The lateral etching may be performed throughthe trench, such as a memory hole, and may occur from sidewalls withinthe trench along an exposed portion of each layer of silicon nitride. Insome embodiments, the lateral etching may be selectively performed onthe silicon nitride layers, and may substantially maintain theintervening layers of silicon oxide or other dielectric material. Method400 may laterally etch the silicon nitride less than 10 nm from thesidewalls of the trench in exemplary operations before the lateraletching operation ends.

Method 400 may involve reducing the etch rate to allow more completediffusion to occur, reducing the adsorption/desorption rates to allowmore complete diffusion to occur, or may involve a type of barrierthrough which the etchant may diffuse at a rate that allows morecomplete diffusion through the trench to occur. For example, method 400may include oxidizing a portion of the silicon nitride to be etched.Because the dielectric layer may be or include silicon oxide, theoxidation may preferentially or exclusively occur on the silicon nitridelayers in regions exposed through the trench, such as forming the trenchsidewalls. The oxidation may include a fluorine or other etchantcomponent, which may diffuse through the oxidized portion to etch thesilicon nitride layers. The fluorinated oxide region of silicon nitrideformed may allow a controlled removal of silicon nitride that is lessthan or about 10 nm from the sidewall of a trench or memory hole.

Precursors used in the method may include a fluorine-containingprecursor as well as an oxygen-containing precursor. An exemplaryfluorine-containing precursor may be nitrogen trifluoride (NF₃), whichmay be flowed into the remote plasma region, which may be separate from,but fluidly coupled with, the processing region. Other sources offluorine may be used in conjunction with or as replacements for thenitrogen trifluoride. In general, a fluorine-containing precursor may beflowed into the remote plasma region and the fluorine-containingprecursor may include at least one precursor selected from the group ofatomic fluorine, diatomic fluorine, nitrogen trifluoride, carbontetrafluoride, hydrogen fluoride, xenon difluoride, and various otherfluorine-containing precursors used or useful in semiconductorprocessing. The oxygen-containing precursor may include a variety offluids, and may include one or more of atomic oxygen, molecular oxygen,N₂O, NO, NO₂, ozone, or other oxygen-containing precursors that may beused or useful in semiconductor processes. The precursors may alsoinclude any number of carrier gases, which may include nitrogen, helium,argon, or other noble , inert, or useful precursors. The carrier gasesmay be used to dilute the precursors, which may further reduce etchingrates to allow adequate diffusion through the trench.

Method 400 may involve tuning the oxygen to fluorine ratio of theprecursors in embodiments. For example, a ratio of oxygen to fluorineprecursors may include a flow rate ratio that is greater than or about20:1 in embodiments. By increasing the oxygen flow rate and limiting thefluorine inclusion, oxidation may occur on the exposed regions ofsilicon nitride prior to the initiation of etching. Accordingly, theoxidation layer may operate similar to a barrier layer through which thefluorine containing etchant may diffuse. The time to diffuse through theoxidation portion of silicon nitride may be greater than the time todiffuse the precursors down through the memory hole or trench. In thisway, an oxidation layer may be formed along each exposed region ofsilicon nitride prior to etching of the regions of silicon nitride. Theetchant may then be uniformly distributed through the trench andoxidation regions allowing a substantially similar amount of etching tooccur on each exposed region of silicon nitride. Similarly, by limitingthe amount of fluorine in the mixture, the amount of material etchedfrom each exposed region of silicon nitride may be controlled.

In exemplary methods, such as method 400, the ratio of oxygen-containingprecursor to fluorine-containing precursor may relate to the thicknessof silicon nitride to be removed. For example, in methods in which moresilicon nitride may be removed, additional fluorine-containing precursormay be included in the precursors, or the time of the operations may beincreased. To provide a lateral etch less than about 10 nm on eachexposed region of silicon oxide within the trench, the ratio ofoxygen-containing precursor to fluorine-containing precursor may begreater than or about 25:1, or may be greater than or about 30:1,greater than or about 35:1, greater than or about 40:1, greater than orabout 45:1, greater than or about 50:1, greater than or about 55:1,greater than or about 60:1, greater than or about 65:1, greater than orabout 70:1, greater than or about 75:1, greater than or about 80:1, orhigher, as well as any smaller range included within any of the statedranges. For example, a flow rate of greater than or about 60:1, mayallow the formation of a fluorinated oxide region on each exposed regionof silicon nitride. The flow rate ratio may be maintained higher than40:1 in embodiments to reduce the amount of silicon nitride etchedthroughout the length of the trench. When the amount of fluorine isincreased in the mixture, regions of silicon nitride at or near the topof the trench may begin to etch before the oxidation portion has formed.This may then still produce a profile within the trench, such as aV-profile of silicon nitride layers from the top to the bottom of thetrench.

The V-profile may be unavoidable with conventional dry technologiesbecause of the high aspect ratios of trenches or memory holes in whichthe lateral etching may be performed. The diameter or width of exemplarytrenches may be a few tens or nanometers or less, while the height ofthe trenches may be on the order or a few microns or more. This mayproduce aspect ratios or height to width ratios of greater than 20:1,greater than 50:1, greater than 75:1, greater than 100:1, or evengreater. Accordingly, in embodiments over 25 layers, over 50 layers,over 75 layers, or over one hundred layers of alternating placeholdermaterial and dielectric material may be formed and processed within eachtrench.

Because of the greater lengths a dry or gaseous etchant may travel, thetop regions of the trench may be exposed to significant amounts ofetchant before the etchant has even reached the bottom of the trench. Inthis way, the silicon nitride located at upper regions of the trench maybe etched more than portions at the bottom of the trench. Although a wetetch technique may more uniformly etch the layers of silicon nitride, itmay be incapable of etching less than 10 or more nanometers because ofthe properties and residence time of the etchant. Accordingly, noconventional technologies may be capable of finely etching an amount ofmaterial from each silicon nitride layer, such as only a few nanometers,as well as produce a flat or substantially similar profile of etchedsilicon nitride throughout the trench, unlike the present technology.The present technology, however, may compensate for the greaterdiffusion pathway by limiting the etchant in any of the ways discussedto allow a more uniform etching process to occur.

Process conditions may also impact the operations performed in method400 as well as other etching methods according to the presenttechnology. Each of the operations of method 400 may be performed duringa constant temperature in embodiments, while in some embodiments thetemperature may be adjusted during different operations. For example,the substrate, pedestal, or chamber temperature during the lateraletching operation 420 may be maintained between about −100° C. and about100° C. in embodiments. The temperature may also be maintained below orabout 80° C., below or about 60° C., below or about 40° C., below orabout 20° C., below or about 0° C., below or about −20° C., below orabout −40° C., or lower. Temperature may affect the etching processitself, and higher temperature may produce higher etch rates, increasedetching, or other effects. Similarly, lower temperatures may slow theetching operation and allow the oxidation of portions of silicon nitrideprior to the etching, or while minimal etching has occurred. Thus, insome embodiments, maintaining a temperature below or about 0° C. mayprovide more uniform etching amounts of silicon nitride at the top ofthe trench and at the bottom of the trench. As temperature increases,the etching operations may additionally begin to affect the dielectricregions, and may cause slight rounding of exposed corners or regions ofthe dielectric material, such as silicon oxide.

The pressure within the chamber may also affect the operationsperformed, and in embodiments the chamber pressure may be maintainedbelow about 10 Torr, below about 5 Torr, or below about 1 Torr. Inembodiments a pressure below or about 1 Torr may allow the precursors orplasma effluents to more easily flow into the trenches or memory holes.However, when the pressure is reduced below about 0.5 Torr, a remoteplasma may be affected, and may have reduced stability or may becomeunstable. As mentioned previously, the remote plasma may include an RPSunit, and may also be a region or portion of the chamber physicallypartitioned from the processing region of the chamber to limit oreliminate plasma at the wafer level. In some embodiments in which an RPSunit is utilized, a choke may be utilized to maintain a higher pressurewithin the RPS unit for plasma stability with a lower pressure within achamber for improved in-trench flow of precursors or plasma effluents.Accordingly, a turbomolecular pump may be utilized in the chamberallowing a chamber pressure down to a few milliTorr, while the RPS ismaintained above or about 0.6 Torr.

The chamber conditions, flow-rate ratio, and other operationalcharacteristics may be adjusted to perform a controlled etch of thesilicon nitride regions. For example, each region of the silicon nitridefrom the trench sidewalls may be etched laterally to a distance or depthless than or about 10 nm. Additionally, the present technology may allowthe silicon nitride to be etched laterally to a distance or depth ofless than or about 9 nm, less than or about 8 nm, less than or about 7nm, less than or about 6 nm, less than or about 5 nm, less than or about4 nm, less than or about 3 nm, less than or about 2 nm, less than orabout 1 nm, or less depending on the thickness of materials to bedeposited. In embodiments each layer of the silicon nitride may beetched to a depth or distance from a trench sidewall of between about 1nm and about 7 nm, or between about 2 nm and about 6 nm.

By performing the operations according to the present technology, theetching power may be reduced relative to the diffusion power of theetchant materials, which may allow a more uniform, substantiallyuniform, or essentially uniform etch to be performed at each siliconnitride region exposed within the trench or memory hole. In embodiments,a silicon nitride region at or near the top of the trench or memoryhole, such as within 2 layers from the top, within 4 layers, within 6layers, within 8 layers, within 10 layers, or more, may have an amountof material etched measured from the sidewall that is similar to asilicon nitride layer or region at or near the bottom of the trench ofmemory hole, such as within 2 layers from the bottom, within 4 layers,within 6 layers, within 8 layers, within 10 layers, or more.

The two layers being compared may be separated by at least 1 layer, atleast 5 layers, at least 11 layers, at least 21 layers, at least 51layers or more depending on the overall number of stacked layers withinthe structure through which the trench or memory hole has been etched.The lateral etch of the two layers being compared may differ by lessthan or about 30%, in terms of the upper layer being etched no more than30% more than the lower layer. Additionally, the present technology mayperform a lateral etch of the two layers so a difference between theamount of silicon nitride etched between the two layers is less than orabout 25%, less than or about 20%, less than or about 15%, less than orabout 10%, less than or about 5%, less than or about 1%, or zerodifference in which case both regions of silicon oxide are etched to anequal depth or distance from a sidewall of the trench.

As noted above, the lateral etch may include oxidizing at portion of thesilicon nitride layers adjacent the trench, and may involve forming afluorinated oxide. The fluorine within or proximate the fluorinatedoxide may diffuse through the layer or oxidized portion during theoperation to laterally etch the silicon nitride or the oxidized portionof the silicon nitride. In some embodiments the method may end at thisstage. For example, this process may partially remove a region of theoxidized silicon nitride adjacent the trench, such as about 1 nm, about2 nm, or more. Accordingly, even if an extent of oxidation haspenetrated further into the silicon nitride, subsequent operations maybe performed because the material may be merely a placeholder, and maysubsequently be removed. However, in some embodiments the method mayfurther include removing the fluorinated oxide from the silicon nitride.These operations will be explained below with respect to FIG. 5, but mayinclude etching the fluorinated oxide with plasma effluents producedfrom a fluorine-containing precursor and a hydrogen-containingprecursor, for example.

FIG. 5 shows exemplary operations in a method 500 according toembodiments of the present technology. Method 500 may include some orall of the operations of method 400 explained above, and may include anyof the components or conditions discussed there. For example, method 500may include flowing a fluorine-containing precursor and anoxygen-containing precursor into a remote plasma region of asemiconductor processing chamber. In some embodiments, one or more ofthe precursors may be flowed into the remote plasma region, while one ormore other precursors may bypass the remote plasma region, and maycontact the plasma effluents subsequent plasma processing. The remoteplasma region may include one or more remote plasma regions including apartitioned region of the processing chamber, or a remote sectionfluidly coupled with the processing chamber. Accordingly, someprecursors may only be excited by contact with other radical components.In other embodiments all precursors may be flowed through the remoteplasma region.

A plasma may be formed of these precursors, which may be primaryprecursors, at operation 505. The plasma may generate primary plasmaeffluents of the fluorine-containing and oxygen containing precursors.The primary plasma effluents may be flowed into a processing region ofthe processing chamber where a substrate is housed. The substrate mayinclude a trench, such as a memory hole, formed through stacked layersincluding alternative layers of silicon nitride and silicon oxide suchas previously described. At operation 510, a portion of the siliconnitride extending from the trench sidewalls may be oxidized by theprimary plasma effluents to produce a fluorinated oxide region in eachlayer of the silicon nitride.

Subsequently, additional operations may be performed within the samechamber in which the oxidation operations were performed. For example,method 500 may further include flowing a fluorine-containing precursorinto the remote plasma region of the semiconductor processing chamberwhile generating a plasma to produce secondary plasma effluents atoperation 515. Operation 515 may include additional precursors, such asa hydrogen-containing precursor. The hydrogen-containing precursor mayinclude hydrogen, a hydrocarbon, water, hydrogen peroxide, or othermaterials that may include hydrogen as would be understood by theskilled artisan. Additional precursors such as carrier gases or inertmaterials may be included with the secondary precursors as well. One ormore of the precursors may be used to produce the secondary plasmaeffluents, and in embodiments some or all of the precursors may bepresent in the remote plasma region to produce the secondary plasmaeffluents. Additionally, one or more of the precursors may bypass theremote plasma region and be flowed into additional regions of theprocessing chamber. These precursors may be mixed with the plasmaeffluents in the processing region or some other region of the chamber.

Once generated, the second plasma effluents may be flowed into theprocessing region of the semiconductor processing chamber where they maycontact the substrate and diffuse within the trench. At operation 520,the oxidized silicon nitride or the fluorinated oxide region may belaterally etched from each layer of silicon nitride. Accordingly, thesilicon nitride may be oxidized to a depth of from about 1 nm to about 8nm, or any other range as previously discussed. Additionally, operation510 may partially etch the silicon nitride layers from the trenchsidewalls, such as to any depth or distance previously noted, but maymaintain a portion of the silicon nitride layers oxidized subsequent theoperation. This oxidized region may be a lower quality oxide than, forexample, the dielectric layers of silicon oxide that may separate thecell regions of the structures. Accordingly, the lateral etchingoperation 520 may involve a process selective to lower quality siliconoxide over higher quality silicon oxide.

As discussed above, the operation may produce substantially uniformetching on the layers of silicon oxide from the top of the trench to thebottom of the trench, also called top to bottom loading. This may allowa layer of silicon nitride at an upper region of the trench and layer ofsilicon nitride at a lower region of the trench to differ in lateraletch amounts by less than about 20% or by any of the differences and/ordepths as previously discussed. The uniformity may occur in part to theconditions in which the operations are performed. For example, aflow-rate ratio of oxygen-containing precursor to fluorine-containingprecursor used to produce the primary plasma effluents may be greaterthan or about 60:1. This may allow an oxidation layer to form, throughwhich the fluorine may diffuse, and which may slow or reduce the etchrate of silicon nitride regions while the precursors are diffusingthrough the trench. Additionally, a temperature within the semiconductorprocessing chamber during the etching method may be less than or about0° C. to further reduce the etch rate occurring.

Turning to FIGS. 6A-6C are shown cross-sectional views of structure 600being processed according to embodiments of the present technology. Asillustrated in FIG. 6A substrate 605 may have plurality of stackedlayers overlying the substrate, which may be silicon, silicon germanium,or other substrate materials. The layers may include IPD layersincluding dielectric material 610, which may be silicon oxide, inalternating layers with placeholder material 620, which may be siliconnitride. Placeholder material 620 may be or include material that willbe removed to produce individual memory cells in subsequent operations.Although illustrated with only 7 layers of material, exemplarystructures may include any of the numbers of layers previouslydiscussed. Trenches 630, which may be memory holes, may be definedthrough the stacked structure to the level of substrate 605. Trenches630 may be defined by sidewalls 632 that may be composed of thealternating layers of dielectric material 610 and placeholder material620.

In FIG. 6B may be illustrated a structure after methods according to thepresent technology have been performed, such as discussed with respectto FIGS. 4-5 above. A portion of each exposed surface of silicon nitridelayers 620 may be oxidized to produce oxidized regions 625. The oxidizedregions may be a fluorinated oxide to etch a portion of the siliconnitride. Although not illustrated, oxidation regions 625 may bepartially recessed from the sidewalls 632 of the trench 630, such as toa distance of up to, about, or greater than about 1 nm, 2 nm, 3 nm, ormore as previously described. The oxidation may not affect dielectriclayers 610, as these layers may already be oxide, for example. However,substrate 605 may include a thin layer of oxidation 627, which may beless than or equal to the depth of oxidation of the silicon nitridelayers 620. In other embodiments the substrate may have minimal orsubstantially no oxidation.

FIG. 6C illustrates a structure after further methods or operationsaccording to the present technology have been performed, such asdiscussed with respect to FIGS. 4-5 above. An etching operation may beperformed to remove the oxidized portions of silicon nitride layers 620.The etching may remove the oxidized portions, which may form a recessedregion of silicon nitride from the trenches 630 and the silicon oxidelayers 610. The layers may be recessed less than about 10 nm, betweenabout 2 nm and about 6 nm, or within any of the ranges discussedelsewhere in this disclosure. Substrate 605 may show minimal etching atthe bottom of trenches 630, and may be reduced by an amount less than orabout 5 nm, and may be reduced to an amount less than or about 3 nm,less than or about 2 nm, less than or about 1 nm, or may besubstantially maintained during the lateral etching operations ofsilicon nitride.

In the preceding description, for the purposes of explanation, numerousdetails have been set forth in order to provide an understanding ofvarious embodiments of the present technology. It will be apparent toone skilled in the art, however, that certain embodiments may bepracticed without some of these details, or with additional details.

Having disclosed several embodiments, it will be recognized by those ofskill in the art that various modifications, alternative constructions,and equivalents may be used without departing from the spirit of theembodiments. Additionally, a number of well-known processes and elementshave not been described in order to avoid unnecessarily obscuring thepresent technology. Accordingly, the above description should not betaken as limiting the scope of the technology. Additionally, methods orprocesses may be described as sequential or in steps, but it is to beunderstood that the operations may be performed concurrently, or indifferent orders than listed.

Where a range of values is provided, it is understood that eachintervening value, to the smallest fraction of the unit of the lowerlimit, unless the context clearly dictates otherwise, between the upperand lower limits of that range is also specifically disclosed. Anynarrower range between any stated values or unstated intervening valuesin a stated range and any other stated or intervening value in thatstated range is encompassed. The upper and lower limits of those smallerranges may independently be included or excluded in the range, and eachrange where either, neither, or both limits are included in the smallerranges is also encompassed within the technology, subject to anyspecifically excluded limit in the stated range. Where the stated rangeincludes one or both of the limits, ranges excluding either or both ofthose included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”,and “the” include plural references unless the context clearly dictatesotherwise. Thus, for example, reference to “a precursor” includes aplurality of such precursors, and reference to “the layer” includesreference to one or more layers and equivalents thereof known to thoseskilled in the art, and so forth.

Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”,“include(s)”, and “including”, when used in this specification and inthe following claims, are intended to specify the presence of statedfeatures, integers, components, or operations, but they do not precludethe presence or addition of one or more other features, integers,components, operations, acts, or groups.

1. An etching method comprising: flowing a fluorine-containing precursorand an oxygen-containing precursor into a processing region of thesemiconductor processing chamber, wherein a substrate is positionedwithin the processing region, and wherein the substrate comprises atrench formed through stacked layers including alternating layers ofsilicon nitride and silicon oxide; and laterally etching the layers ofsilicon nitride from sidewalls of the trench while substantiallymaintaining the layers of silicon oxide, wherein the layers of siliconnitride are laterally etched less than 10 nm from the sidewalls of thetrench, and wherein a temperature within the processing region ismaintained below about 0° C.
 2. The etching method of claim 1, wherein aflow-rate ratio of oxygen-containing precursor to fluorine-containingprecursor is greater than or about 50:1.
 3. The etching method of claim1, wherein the stacked layers comprise at least 50 layers of alternatinglayers of silicon nitride and silicon oxide, and wherein the trench ischaracterized by an aspect ratio of greater than or about 100:1.
 4. Theetching method of claim 1, wherein the lateral etching is performed at atemperature below about −20° C.
 5. The etching method of claim 1,wherein the lateral etching is performed at a chamber operating pressureof less than or about 1 Torr.
 6. The etching method of claim 1, whereinthe layers of silicon nitride are laterally etched less than or about 6nm.
 7. The etching method of claim 1, wherein the lateral etchingcomprises oxidizing a portion of the silicon nitride to produce afluorinated oxide.
 8. The etching method of claim 7, wherein fluorinewithin the fluorinated oxide diffuses through the oxidized portion ofthe silicon nitride to laterally etch the silicon nitride.
 9. Theetching method of claim 7, wherein the method further comprises removingthe fluorinated oxide from the silicon nitride.
 10. The etching methodof claim 9, wherein removing the fluorinated oxide comprises etching thefluorinated oxide with plasma effluents produced from afluorine-containing precursor and a hydrogen-containing precursor. 11.The etching method of claim 1, wherein a layer of silicon nitride at anupper region of the trench and a layer of silicon nitride at a lowerregion of the trench differ in lateral etch amounts by less than about30%.
 12. An etching method comprising: flowing a fluorine-containingprecursor and an oxygen-containing precursor into a remote plasma regionof a semiconductor processing chamber; forming a plasma within theremote plasma region to generate primary plasma effluents of thefluorine-containing and oxygen-containing precursors; flowing theprimary plasma effluents into a processing region of the semiconductorprocessing chamber, wherein a substrate is positioned within theprocessing region, and wherein the substrate comprises a trench formedthrough stacked layers including alternating layers of silicon nitrideand silicon oxide; oxidizing a portion of the silicon nitride fromsidewalls of the trench to produce a fluorinated oxide region in eachlayer of silicon nitride; flowing a fluorine-containing precursor intothe remote plasma region of the semiconductor processing chamber whilegenerating a plasma to produce secondary plasma effluents; flowing thesecondary plasma effluents into the processing region of thesemiconductor processing chamber; and laterally etching the fluorinatedoxide region from each layer of silicon nitride.
 13. The etching methodof claim 12, wherein a flow-rate ratio of oxygen-containing precursor tofluorine-containing precursor used to produce the primary plasmaeffluents is greater than or about 60:1.
 14. The etching method of claim12, wherein the silicon nitride is oxidized to a depth of from about 1nm to about 8 nm.
 15. The etching method of claim 12, wherein a bottomof the trench is at least partially oxidized along with the layers ofsilicon nitride, and wherein the bottom of the trench is etched lessthan or about 5 nm.
 16. The etching method of claim 12, wherein atemperature within the semiconductor processing chamber during theetching method is less than or about 0° C.
 17. The etching method ofclaim 12, wherein laterally etching the fluorinated oxide region fromeach layer of silicon nitride further comprises flowing ahydrogen-containing precursor into the semiconductor processing chamber.18. The etching method of claim 12, wherein the oxidized portion ofsilicon nitride comprises a lower quality oxide than the layers ofsilicon oxide.
 19. The etching method of claim 12, wherein a layer ofsilicon nitride at an upper region of the trench and a layer of siliconnitride at a lower region of the trench differ in lateral etch amountsby less than about 20%.